WO2014037627A1

WO2014037627A1 - Process for manufacturing press-hardened coated steel parts and precoated sheets allowing these parts to be manufactured

Info

Publication number: WO2014037627A1
Application number: PCT/FR2012/000350
Authority: WO
Inventors: Juan David PUERTA VELASQUEZ; Jonas STAUDTE; Pascal Drillet
Original assignee: Arcelormittal Investigación Y Desarrollo Sl
Priority date: 2012-09-06
Filing date: 2012-09-06
Publication date: 2014-03-13
Also published as: CA2895944C; MX366129B; EP2893047A1; IN2015DN01908A; JP2016504488A; US20160017452A1; US20170260599A1; BR112015005090A8; MX2015002972A; FI3783118T3; BR112015005090B8; HUE062051T2; RU2610995C2; UA115791C2; EP3783116A1; BR112015005090B1; PL2893047T3; PL3783118T3; US9909194B2; BR112015005090A2

Abstract

The invention relates to a precoated laminated sheet for manufacturing press-hardened parts, which sheet is composed of a steel substrate for heat treatment, which substrate has a carbon content C₀ comprised between 0.07% and 0.5%, said content being expressed by weight, and a metal precoating at least on the two main faces of said steel substrate, characterised in that said substrate comprises a decarbonated zone on the surface of each of its two main faces, the depth p_50% of said decarbonated zone being comprised between 6 and 30 microns, p_50% being the depth at which the carbon content is equal to 50% of said content C₀, and in that said sheet does not contain an iron oxide layer between said substrate and said metal precoating.

Description

PROCESS FOR MANUFACTURING COATED AND PRESSURE-CURED STEEL PARTS, AND PREFERRED SHEETS FOR PERMITTING

THE MANUFACTURE OF THESE PIECES

The invention relates to a method of manufacturing parts from pre-coated steel sheets, heated, stamped and hardened during cooling obtained by holding in a press tool; these parts are particularly intended to be used as structural elements in motor vehicles to provide anti-intrusion or energy absorption functions. Such parts can also be used for example for the manufacture of tools or agricultural machinery parts.

In this type of application, it is sought to produce steel parts combining high mechanical strength, high impact resistance, good resistance to corrosion, and good dimensional accuracy. This combination is particularly desirable in the automotive industry where significant vehicle lightening is sought. Anti-intrusion parts or parts involved in the safety of motor vehicles such as bumper rails, reinforcements door or center stand, require for example the qualities mentioned above. This can be achieved in particular by steel pieces whose microstructure is martensitic or bainito-martensitic.

The manufacture of such parts is known from publications FR2780984 and FR2807447 according to which a blank cut from a sheet of steel for heat treatment, pre-coated with a metal or a metal alloy, is heated in an oven and then hot deformed. The pre-coating may be aluminum or an aluminum alloy, zinc or a zinc alloy. When heated in an oven, the pre-coating protects the surface of the steel against decarburization and scale formation. During furnace heating, this pre-coating is combined with the steel substrate to form a hot-forming compound which does not cause degradation of the tooling. The maintenance of the part in the tooling after the shaping has been carried out, allows rapid cooling which leads obtaining quenching microstructures having very high mechanical characteristics. Such a process is known as hardening by press hardening.

As a general rule, the mechanical properties of the parts thus obtained are evaluated by means of tensile and hardness tests. The aforementioned documents thus disclose manufacturing methods for obtaining a mechanical strength (or tensile strength) Rm of 1500 MPa from a steel blank having an initial resistance Rm of 500 MPa before heating and cooling fast.

However, the service conditions of some cured and coated parts require not only a high value of resistance Rm, but also good bendability. This parameter appears indeed to be more relevant than the tensile elongation measured in tension, to ensure that the part has a ductility sufficient to absorb deformations or shocks without risk of rupture, especially in areas corresponding to local concentrations of stress due to the geometry of the part or the possible presence of micro-defects on the surface of the parts.

WO2009080292 discloses a method for increasing the bending angle of a cured part: according to this method, a steel sheet is heated in an annealing furnace at a temperature between 650 and 800 ° C so as to obtain an oxide layer with a thickness substantially greater than 0.3 micrometers. Some alloying elements of steel are oxidized under this oxide layer. This oxide layer is then partially reduced so that it has a thickness greater than 0.3 micrometers. The extreme surface of the reduced oxide layer consists of pure iron. The sheet is then tempered. After this step, the sheet comprises the following successive layers: the steel substrate comprising oxidized elements in the vicinity of the surface (internal oxidation), this substrate being surmounted by a partially reduced oxide layer, itself surmounted by dip coating. In the subsequent step of austenitizing the blank, and / or during shaping and cooling, a thin ductile layer is formed under the coating, so that the cracks formed during the coating during shaping propagate less easily in this underlying layer.

However, the oxide layer that is present at the moment when the sheet is immersed in the coating metal bath, may be detrimental to the adhesion of the coating to dipping on this layer.

A method of manufacture is therefore sought which does not have this drawback and which would make it possible simultaneously to obtain, after hardening by quenching in press, high tensile and folding characteristics. In addition, it is known that the industrial manufacturing conditions inevitably include a certain variability: for example, the temperature cycle during the annealing of the sheet before coating, the composition and / or the dew point of the furnace atmosphere. continuous annealing, may vary slightly during the same production sequence, or vary from one manufacturing campaign to another. Even if the greatest precautions are taken to minimize these variations, it is sought to have a manufacturing method such that the mechanical characteristics, and in particular the folding ability, obtained after hardening by press quenching, are very insensitive to this possible variation of the manufacturing conditions. In addition, a manufacturing process is sought that leads to good isotropy of the parts after hot stamping, that is to say whose folding ability depends little on the direction of loading relative to the rolling direction of the sheet.

In addition, it is known that the residence time of the blanks in the furnaces, during the austenitization step before hot stamping, can influence the mechanical characteristics of the parts. It is therefore sought to have a manufacturing method that is insensitive to the holding time in the oven in order to obtain a high reproducibility of the mechanical characteristics of the parts.

In the case of parts made from sheets pre-coated with zinc or zinc alloy, it is sought to have a method for welding these parts without the risk of embrittlement of the grain boundaries by penetration of the liquid zinc . The present invention aims to solve the problems mentioned above by means of an economical manufacturing process.

Surprisingly, the inventors have demonstrated that a high ability to bend parts, was obtained when a decarburized zone of a specific thickness was present under the metal pre-coating, before hardening by press-hardening of the room. Surprisingly, this specific decarburization before hardening leads to folding results which are not very dependent on continuous annealing conditions before coating, and which reflect good isotropy with respect to the rolling direction.

For this purpose, the subject of the invention is a pre-coated rolled sheet for the manufacture of parts hardened by press quenching, composed of a steel substrate for heat treatment containing a carbon content C ₀ of between 0.07 and % and 0.5%, this content being expressed by weight, and a metal pre-coating at least on the two main faces of the steel substrate, characterized in that the substrate has a decarburized zone on the surface of each of the two main faces, the depth p _50% of the decarburized zone being between 6 and 30 micrometers, pso being the depth at which the carbon content is equal to 50% of the content C ₀ , and in that the sheet does not contains no iron oxide layer between the substrate and the metal pre-coating. The depth p ₅ o _% of the decarburized zone is advantageously between 9 and 30 micrometers, and very advantageously between 12 and 30 micrometers.

In a preferred embodiment, the metal pre-coating of the sheet is aluminum or an aluminum alloy.

According to another preferred embodiment, the metal pre-coating is zinc or a zinc alloy.

The metal pre-coating may preferably be composed of a layer of aluminum or of an aluminum alloy, surmounted by a layer of zinc or a zinc alloy.

The composition of the steel substrate advantageously comprises the contents being expressed by weight: 0.07% <C <0.5%, 0.5% <Mn <3%, 0.02% <Si < 0.5%, 0.01% <Cr <1%, Ti <0.2%, Al <0.25%, S <0.05%, P <0.1%, 0.0005% <B < 0.010%, optionally 0.0005% <Ca <0.005%, the rest of the composition consisting of iron and unavoidable impurities resulting from the preparation.

Very advantageously, the composition of the steel substrate comprises, the contents being expressed by weight: 0.09% <C <0.38%, 0.8% <Mn <1.5%, 0.1% <Si < 0.35%, 0.01% <Cr <0.3%, 0.02% <Ti <0.1%, 0.001% ≤ Al <0.25%, S <0.05%, P <0, 1%, 0.002% <B <0.005%, optionally 0.0005% <Ca <0.005%, the remainder of the composition consisting of iron and unavoidable impurities resulting from the preparation.

According to a preferred embodiment, the composition of the steel substrate comprises, the content being expressed by weight: 0.15% <C <0.25%

The subject of the invention is also a process for producing a coated and cured steel part, comprising the successive stages in which a laminated steel sheet for heat treatment is supplied containing a carbon content C ₀ between 0.degree. 07% and 0.5%. The rolled sheet is annealed so as to obtain at the end of the annealing a decarburization of the surface of the sheet to a depth p ₅₀ % of between 6 and 30 microns, p ₅ o% being the depth at which the carbon content is equal to 50% of said content C ₀ , and so as to obtain a sheet completely free of iron oxide layer on its surface, then a pre-coating of metal or metal alloy is carried out on said annealed sheet playing the role of substrate. The pre-coated sheet is then cut to obtain a blank, then the blank is optionally cold-pressed, and then heated to a temperature T _R in an oven so as to at least partially impart an austenitic structure to said steel. . The heated blank is extracted from the furnace and transferred to a press or a shaping device, then hot deformed or heat calibrated blank to obtain a coin that is cooled in the press or the shaping device for quenching it with a martensitic or bainitomensitic microstructure. The invention also relates to a manufacturing process characterized in that the pre-coating is carried out continuously by dipping by passing through a bath.

In a preferred embodiment, the pre-coating is aluminum or an aluminum alloy.

The pre-coating is preferably zinc or a zinc alloy.

In a particular embodiment, the metal pre-coating is composed of a layer of aluminum or an aluminum alloy, surmounted by a layer of zinc or a zinc alloy.

The depth p _50% is advantageously between 9 and 30 micrometers, preferably between 12 and 30 micrometers

The invention also relates to a process characterized in that the composition of the steel substrate comprises, the contents being expressed by weight: 0.07% <C <0.5%, 0.5% <Mn <3% , 0.02% <If <0.5%, 0.01% <Cr <

1%, Ti <0.2%, Al <0.25%, S <0.05%, P <0.1%, 0.0005% <B <0.010%, optionally 0.0005% <Ca <0.005 %, the rest of the composition being made of iron and unavoidable impurities resulting from the elaboration.

According to a particular mode of the process, the composition of the steel substrate comprises, the contents being expressed by weight: 0.09% <C <0.38%, 0.8% <

Mn <1, 5%, 0, 1% <Si <0.35%, 0.01% <Cr <0.3%, 0.02% <Ti <0.1%, 0.001%

<Al <0.25%, S <0.05%, P <0.1%, 0.002% <B <0.005%, optionally

0.0005% <Ca <0.005%, the balance of the composition consisting of iron and unavoidable impurities resulting from the elaboration.

According to a particular mode of the process: 0, 15% <C <0.25%.

The temperature TR is preferably greater than or equal to the temperature A _C 3 of the steel.

The subject of the invention is also a manufacturing method according to any one of the modes set out above, the annealing conditions of which comprise the following successive stages: after having supplied the rolled steel sheet, the parcel is preheated in a a radiant tube furnace, or a resistance furnace, or an induction furnace, or an oven combining at least two of these means, the rolled sheet to a temperature T1a between 600 ° C and Ac1 + 40 ° C, where Ac1 denotes the austenitic transformation start temperature when heating the steel, in a zone of the furnace where the atmosphere A1 contains from 2 to 15% by volume of hydrogen preferably 3-5% by volume of hydrogen, the balance being nitrogen and unavoidable impurities, with a dew point between -60 and -15 ° C. The sheet of temperature T1a is then heated to a temperature T2a of between 720 and 860 ° C., an injection of at least one element chosen from liquid water, steam water or oxygen. being carried out in the oven from the temperature T1a to obtain, in the furnace section between the temperature T1a and the temperature T2a, an atmosphere A2a with a dew point PR of between -15 ° C. and the temperature Te of the point dew point of the equilibrium Iron / iron oxide, the time interval between the instant when the sheet is at the temperature T1a and the instant when the sheet reaches the temperature T2a, being greater than or equal to 30 seconds. The sheet is then maintained at a temperature Tm between T2a and T2a + 40 ° C, under a reducing atmosphere A3 for iron, and then cooled in an atmosphere A4 such that no surface reoxidation of the iron intervenes, up to a temperature T3. The sheet is then pre-coated with a dip in a metal bath at the temperature Tbm, with the proviso that the temperature T3 is between Tbm-10 ° C and Tbm + 50 ° C.

Preferentially, the dew point PR of the atmosphere A2a is between -15 and + 17 ° C., very preferably between -15 and -10 ° C.

The invention also relates to a manufacturing method whose annealing conditions comprise the following successive steps: after supplying the rolled steel sheet, is preheated on parade in a radiant tube furnace, or a resistance furnace, or an induction furnace, or a furnace combining at least two of these means, the rolled sheet to a temperature T1a between 600 ° C and Ac1 + 40 ° C, Ac1 designating the austenitic transformation start temperature to the heating of steel, in an area of the furnace where the atmosphere A1 contains from 2 to 15% by volume of hydrogen, preferably 3-5% by volume of hydrogen, the balance being nitrogen and unavoidable impurities, with a dew point between -60 and -15 ° C. The sheet of temperature T1a is then heated to a temperature T2a of between 720 and 860 ° C., an injection of at least one element chosen from liquid water, steam water or oxygen. being carried out in the oven from the temperature T1a to obtain, in the furnace section between the temperature T1a and the temperature T2a, an oxidizing atmosphere A2b for the iron, the time interval between the instant when the sheet is at the temperature T1a and the instant when the temperature reaches the temperature T2a, being greater than or equal to 30 seconds. The sheet is then maintained at a temperature Tm between T2a and T2a + 40 ° C, under a reducing atmosphere A3 for iron, the complete reduction of the iron layer formed in said atmosphere A2b, occurring at the latest at the end of maintaining the temperature Tm. The sheet is then cooled in an atmosphere A4 such that no superficial reoxidation of the iron takes place, up to a temperature T3, and then the sheet is pre-coated by a dipping step in a metal bath at the temperature Tbm, it being understood that the temperature T3 is between Tbm-10 ° C and Tbm + 50 ° C

According to an advantageous embodiment, the temperature T1a is greater than Ac1, that is to say the austenitic transformation temperature when heating the steel substrate.

The subject of the invention is also a manufacturing method whose annealing conditions comprise the following successive stages: after supplying a steel sheet, the laminated sheet is preheated in an oven, the preheating being carried out in a zone of a heated oven with direct flames, the sheet being preheated to a temperature T1b between 550 and 750 ° C in an atmosphere resulting from the combustion of a mixture of air and natural gas whose air / gas ratio is between 1 and 1, 2. The sheet of the temperature T1b is heated to a temperature T2b of between 760 and 830 ° C. in a second oven zone heated by radiant tubes, or by resistance, or by induction, or by any combination of at least two of these means, the atmosphere of which contains from 3 to 40% by volume of hydrogen, the balance being nitrogen and unavoidable impurities, the dew point being lower than -30 ° C, the time interval between the moment when the sheet is at the temperature T1 b and the moment when the latter reaches the temperature T2b, being at least 30 seconds. The sheet is maintained at a temperature Tm of between T2b and T2b + 40 ° C., under a reducing atmosphere A3 for iron, and then the sheet is cooled in an atmosphere such that no surface reoxidation takes place, up to a temperature T3. Pre-coating of the sheet metal is carried out by dipping in a metal bath at the temperature Tbm, it being understood that the temperature T3 is between Tbm-10 ° C and Tbm + 50 ° C.

In a preferred embodiment, the temperature T2b is greater than Ac1.

Other features and advantages of the invention will become apparent from the following description given by way of example and with reference to the following appended figures:

FIG. 1 shows the microstructure of a pre-coated steel sheet according to the invention, intended for the manufacture of hardened parts by quenching in a press.

FIG. 2 schematically illustrates the definition of the depth of the softened area d measured by microhardness under the coating of a hardened part by press quenching.

3 schematically shows the definition for a sheet or a precoated blank, the depth of decarburization of the surface p ₅ _{o% as} measured by spectroscopy glow discharge under the pre-coating of the sheet or blank before hardening by press hardening.

FIG. 4 shows the variation of the critical bending angle a _c of a press hardened coated part, as a function of the depth of the surface softened area, which is measured by microhardness under the coating.

FIG. 5 shows the variation of the critical bending angle a _c of a pressed quench-hardened coated part, as a function of the _50% decarburization depth, which is measured on the pre-coated blank before stamping. hot and quenched.

Figure 6 shows the influence of the dew point in a particular area of the oven during annealing before pre-coating, on the critical angle of folding of the workpiece after hot stamping.

FIG. 7 shows the influence of the dew point in a particular zone of the oven during annealing before precoating, on the decarburization depth P 50%, the latter parameter being measured on the pre-coated blank before hot stamping and quenching.

Figure 8 shows the microstructure of the steel under the zinc coating, after hardening by press quenching, for a dew point of -27 ° C.

Figure 9 also illustrates the microstructure of the steel under the zinc coating, after hardening by press quenching, for a dew point of -7 ° C.

FIG. 10 illustrates the variation, before hot stamping, of the carbon content of the steel substrate of two pre-coated steel sheets, in the vicinity of their interface with the pre-coating, the annealing of the sheets having been carried out in an A2a atmosphere with a dew point of -27 ° C or -7 ° C.

FIG. 11 illustrates the variation of the carbon content of two pieces of hot-stamped steel, in the vicinity of the interface with the coating of these parts, the annealing of the sheets used for the manufacture of these parts having been carried out in a A2a atmosphere with a dew point of -27 ° C or -7 ° C.

The thickness of the steel sheet used in the process according to the invention is preferably between 0.5 and 4 mm, thickness range used in particular in the manufacture of structural parts or reinforcement for the industry. automobile.

Steel is a steel for heat treatment, that is to say a steel capable of hardening after austenitization and quenching fast cooling. Advantageously, the steel contains the following elements, the composition being expressed by weight:

a carbon content of between 0.07 and 0.5%, preferably between 0.09 and 0.38% by weight, and very preferably between 0.15 and 0.25% by weight. This element plays a major role in the quenchability and the mechanical strength obtained after cooling after treatment austenitizing. Below a content of 0.07% by weight, the quenchability is reduced and the mechanical strength is insufficient after quenching in press. A content of 0.15% C ensures sufficient quenchability in the most hot deformed areas. Beyond a content of 0.5% by weight, the risk of formation of defects is increased during quenching, particularly for thicker parts. It also becomes difficult to guarantee ductility when folding parts after hardening by press-hardening. A carbon content of between 0.09 and 0.38% makes it possible to obtain a resistance Rm of between approximately 1000 and 2050 MPa when the microstructure of the part is totally martensitic.

in addition to its deoxidizing role, manganese also has a significant effect on quenchability, in particular when its content by weight is greater than 0.5%, and preferably greater than 0.8%. However, it is preferable to limit its addition to 3% by weight, and very preferably to limit it to 1.5% so as to avoid excessive segregation.

the silicon content of the steel must be between 0.02 and 0.5% by weight, and preferably between 0.1 and 0.35%. In addition to its role in the deoxidation of liquid steel, this element contributes to the hardening of the steel, but its content must be limited, however, to avoid the excessive formation of oxides and not to impair the coating ability by dipping.

- Beyond a content greater than 0.01%, chromium increases the quenchability and contributes to obtaining significant resistance after the hot forming operation. Beyond a content equal to 1% (preferentially 0.3%), the effect of chromium on the homogeneity of the mechanical properties in the part is saturated.

aluminum is an element promoting the deoxidation and the precipitation of nitrogen. In excessive amounts, coarse aluminates are formed during processing which tend to reduce the ductility, which makes it possible to limit the aluminum content to 0.25% by weight. A minimum content of 0.001% makes it possible to deoxidize the steel in the liquid state during the preparation.

In excessive amounts, sulfur and phosphorus lead to increased brittleness. Therefore, it is preferable to limit their respective content to 0.05 and 0.1% by weight.

boron, the content of which must be between 0.0005 and 0.010% by weight, and preferably between 0.002 and 0.005% by weight, is an element which plays an important role on the quenchability. Below a 0.0005% content, a sufficient effect on the quenchability is not obtained. The full effect is obtained for a content of 0.002%. The maximum boron content must be less than 0.010%, and preferably 0.005%, in order not to degrade the tenacity.

Titanium has a high affinity for nitrogen. It protects the boron so that this element is in free form to play its full effect on the hardenability. Above 0.2%, however, there is a risk of forming coarse titanium nitrides in the liquid steel which play a detrimental role on toughness. It is preferably between 0.02 and 0.1%.

- As an option, the steel can also contain calcium in a quantity between 0.0005 and 0.005%: by combining with oxygen and sulfur, calcium makes it possible to avoid the formation of large inclusions which are harmful to the ductility of the sheets or parts thus manufactured.

The rest of the composition of the steel consists of iron and unavoidable impurities resulting from the elaboration.

A preferred steel is 22MnB5 containing 0.20-0.25% C, 1, 1 -1, 35% Mn, 0.15-0.35% Si, 0.02-0.06% AI, 0.02 -0.05% Ti, 0.02-0.25% Cr, 0.002-0.004% B, the balance being iron and unavoidable impurities.

The inventors first sought the conditions which made it possible to obtain a good folding ability after hardening by press-hardening. This characteristic is measured by subjecting the part to a three-point bending. The workpiece is progressively folded over three-point bending rolls, the applied load being measured simultaneously. The critical bending angle a _c is measured during the occurrence of cracks in the workpiece, which is accompanied by an instantaneous decrease in the applied load. Such test conditions are described in DIN VDA 238-100. For a breaking load Rm of the order of 1300-1600 MPa, a critical bending angle greater than 55 ° is required in order to meet the specifications. We even preferentially seek a folding angle critical greater than 60 ° to satisfy more severe conditions of use.

By means of a manufacturing method which will be detailed below, the inventors have manufactured parts, from blanks of 22MnB5 steel of 1, 2mm thick pre-coated with zinc galvanized-alloyed ("galvannealed"), hot stamped after heating at 880 ° C. and holding for 5 minutes, differing only in the presence of a softened layer of greater or lesser extent located under the coating. The method for determining the depth of this softened zone is diagrammatically illustrated in FIG. 2: after hardening by press quenching, the part consists of a heat treatment steel substrate 6, a coating 4 separated from the substrate by the interface 5. Note that this diagram is not intended to reproduce the respective dimensions of the different areas. Hardness measurements are made under a very light load (for example Vickers hardness under a load of 50 grams, HV0.05) in the substrate from the interface 5, so as to obtain the curve 7 illustrating the profile of microhardness. We deduce the value d which characterizes the depth of the softened zone. FIG. 4 shows the critical bending angle α _c measured for values of d varying approximately between 30 and 40 microns. For a low softened area depth, hot stamped parts do not meet the requirement at _c > 55 °. However, for deeper softened areas, it is observed that the relationship is tainted by a large dispersion: for a given value of d, for example 35 micrometers, it is not possible to determine with certainty if the hot-stamped part satisfy the required criterion. It has also been observed that the microstructures corresponding to these softened zones of variable width are very similar after hardening by press quenching. In addition, the microstructure of these softened zones can be completely martensitic, that is to say that it is not possible to easily distinguish it by conventional optical microscopy. In other words, the inventors have demonstrated that neither the depth of the softened areas measured on the parts cured by press quenching, nor the optical microstructural observation of the softened areas of these parts, are parameters to reliably guarantee a minimum value for the bending angle.

Surprisingly, the inventors have demonstrated that it was necessary to determine, not on the part hardened by press quenching, but on the pre-coated sheet or blank before curing, the depth of decarburization, to obtain the desired result. The determination method is illustrated in FIG. 3, the diagram of which is not intended to reproduce on a scale the respective dimensions of the different zones: the sheet or the blank consists of a steel substrate 10, a meadow coating 8 separated from the substrate by the interface 9. From this interface is measured by glow discharge spectroscopy (or GDOES, "Glow Discharge Optical Emission Spectrometry technique known in itself) the depth p _50% to which carbon content is equal to 50% of the nominal carbon content C ₀ of the substrate 10. The concentration profile may exhibit a regular decrease in carbon from the substrate to the interface (profile 1 1) or a The latter case represents a localized carbon enrichment in the vicinity of the extreme surface which has no influence in practice on the mechanical properties after hot stamping. In the case of the profile 12, the depth pso% to be taken into account is beyond this very superficial enrichment, as shown in FIG. 3. Thanks to a manufacturing process which will be detailed below, the inventors have manufactured 22MnB5 sheet of 1, 2mm thick pre-coated zinc galvanized-alloyed ("galvannealed") differed by the presence of a decarburized layer more or less important under the pre-coating. These sheets were cut to obtain blanks that were heated in an oven at 880 ° C for 5 minutes, then hot stamped to obtain parts. These were subjected to folding tests, the results of which are illustrated in FIG. 5, the flexion during bending being in a direction parallel to the direction of rolling (curve 13) or in a perpendicular direction (curve 14). ). Contrary to the results presented in FIG. 4, it is observed that the depth of the decarburized zone before hardening by press hardening makes it possible to predict satisfactory properties of the part after hardening by quenching in press. To obtain a critical bending angle value at _c ≥ 55 ° (bending direction parallel to rolling), the depth of the decarburized zone p _50% must not be less than 6 micrometers. For this condition to be fulfilled irrespective of the orientation with respect to the rolling direction, the depth of decarburization p _50% must not be less than 9 microns. To obtain a value at _c ≥ 55 °, irrespective of the orientation with respect to the rolling direction, the decarburization depth p _50% must not be less than 12 micrometers. Surprisingly, however, it is observed that beyond a depth of _50% of 30 micrometers, the folding ability is not improved or even slightly decreased when the flexion is exerted in the perpendicular direction. rolling. In addition, the deviation of the folding ability between the direction parallel to the direction perpendicular to the rolling tends to increase. Thus, to satisfy the mechanical requirements, the value of p _50% must be between 6 and 30 microns, preferably between 9 and 30, and very preferably between 12 and 30 microns.

The process according to the invention will now be described: a steel for heat treatment is first supplied, as indicated above. This may be in the form of hot-rolled or subsequently cold-rolled sheet. After optional degreasing and electrolytic cleaning to obtain a pollution-free surface, a _50% decarburization depth of between 6 and 30 microns can be obtained by the following methods:

according to a first embodiment, the sheet is subjected to a heat treatment on the parade in a furnace heated by means of radiant tubes (or "RTF", radiant tube furnace), or by resistance, or by induction, or by any combination of these different ways. These have the characteristic that the atmosphere prevailing in the different parts of the furnace can be adjusted independently of these heating means. The furnace comprises several zones (preheating, heating, holding, cooling) where different temperature and / or atmosphere conditions prevail: the sheet is preheated to a temperature T a in an area where the atmosphere (designated A1) contains from 2 to 15% by volume of hydrogen, preferably 3-5% by volume of hydrogen, the balance being nitrogen and unavoidable impurities in the gas, with a point of dew between -60 and -15 ° C. It is known that the dew point characterizes the oxidation potential of the atmosphere in question. The scrolling sheet then passes into another zone of the furnace where injection is made from a temperature T1a, water in liquid form or in vapor form, or oxygen, or a combination of these. different elements, so as to increase the dew point of the atmosphere. The injection must not be carried out at a temperature T1 to less than 600 ° C which would lead to an oxidation of iron at low temperature. Preferably, the injection is carried out at a temperature T1a greater than Ad, austenitic transformation start temperature of the steel heating. Indeed, beyond this temperature, the carbon is in solid solution in the austenite, that is to say in a form more suitable for the decarburizing phenomenon that will occur. The injection is carried out preferentially at a temperature T1 a less than or equal to Ac1 + 40 ° C. This temperature range greater than Ac1 will be preferred to obtain a decarburization depth p ₅ o greater, for example greater than 9 or 12 micrometers. Beyond Ac1 + 40 ° C, there is a risk of increasing the austenitic grain size and causing the formation of bainitic and / or martensitic compounds in the steel substrate during cooling following annealing.

The injection is carried out so that the dew point PR of the atmosphere A2a of this section of the furnace is between -15 ° C and the temperature Te of the dew point of the thermodynamic equilibrium Iron / iron oxide . In the temperature range under consideration, the iron oxide formed may be FeO or Fe3O4. We will choose the lowest equilibrium temperature Te corresponding to the formation of one or the other oxide. This temperature Te can be determined for example from the publication: JANAF Thermomechanical Tables, 3rd Edition, Part II, Journal of Physical and Chemical Reference Data, Volume 14, 1985, Supplement No. 1, published by the American Chemical Society and The American Institute of Physics for the National Bureau of Standards. In these conditions of injection, one creates a selective internal oxidation of certain additive elements present in the steel (Mn, Si, Al, Cr, Ti, C) without any superficial oxidation of the iron. The internal oxidation may have a depth of up to about 40 microns below the surface for carbon, and up to about 5 micrometers below the surface for Mn, Si, Al and Cr. Superficial decarburization occurs under these conditions. When the dew point is greater than the dew point temperature Te corresponding to the iron / iron oxide equilibrium, the atmosphere becomes oxidizing to iron. In subsequent annealing steps, there is then a possible risk of not completely reducing the iron oxide and causing the local appearance of coating defects corresponding to the local presence of unreduced surface oxides. The temperature Te is a function of the temperature and the hydrogen content of the atmosphere. As an indication, for an atmosphere containing 97.5% nitrogen and 2.5% hydrogen, Te = + 9 ° C at 800 ° C. For an atmosphere containing 95% nitrogen and 5% hydrogen, Te = + 18 ° C at 800 ° C. The sheet then leaves the section in which the injection was performed at a temperature T2a of between 720 and 860 ° C. to enter a holding zone at a temperature Tm between T2a and T2a + 40 ° C. The time interval between the instant when the sheet is at temperature T1a and the moment when it reaches temperature T2a, must be at least 30 seconds in order to obtain a decarburization depth p ₅₀ % between 6 and 30 micrometers.

Optionally, the atmosphere in the beginning of the holding zone may be identical to that of the previous zone, that is to say having a dew point between -15 and Te. The sheet can then be cooled or maintained at a temperature Tm under an atmosphere A3 containing from 2 to 15% by volume of hydrogen, preferably 3-5% by volume of hydrogen, the balance being from nitrogen and unavoidable impurities in the gas, with a dew point between -60 and -15 ° C, these conditions being reducing for iron. The following cooling step will be described below.

According to a second mode, the manufacturing process is started in the same manner as the one just described up to the injection stage of the invention. T1a temperature between 600 ° C and Ac1 + 40 ° C, preferably greater than Acl At this temperature, an amount of water, steam or oxygen is injected so as to obtain in this zone of the furnace an atmosphere designated by A2b , oxidizing for iron. These conditions cause a total oxidation of the surface, that is to say iron and some elements of addition (Mn, Si, Al, Cr, Ti, C) A superficial decarburization intervenes at the same time as the oxidation iron. The sheet then leaves the injection section at a temperature T2a between 720 and 860 ° C to enter a holding zone at a holding temperature Tm between T2a and T2a + 40 ° C. The time interval between the instant when the sheet is at temperature T1a and the moment when it reaches temperature T2a, must be at least 30 seconds in order to obtain a decarburization depth p ₅₀ % between 6 and 30 micrometers. Beyond this, in the holding zone, the sheet is maintained at the temperature Tm in a reducing atmosphere A3 for the iron, the conditions being chosen in such a way that the complete reduction of the iron oxide layer takes place at the latest at the end of maintaining the temperature Tm. For example, an atmosphere containing from 2 to 15% by volume of hydrogen, preferably 3-5% by volume of hydrogen, the balance being nitrogen, may be selected for this purpose. and unavoidable impurities in the gas with a dew point between -60 and -15 ° C, for a time long enough for a complete reduction of the iron oxide surface layer to occur in this zone. The following cooling step will be described below. according to a third mode, the annealing thermal cycle of the sheet combines different heating means; the preheating step is performed in an area of a direct flame heated furnace (or "DFF"): the sheet is preheated to the parade to a temperature T1b between 550 and 750 ° C in an area where the atmosphere results from the combustion of a mixture of air and natural gas. According to the invention, the air / gas ratio is between 1 and 1, 2, it being understood that the air-gas combustion in a stoichiometric ratio is 1. These preheating conditions lead to the formation of a surface layer of iron oxide of which the thickness is between 0.10 and 0.25 micrometers. At the outlet of this preheating zone by furnace DFF, the sheet enters a second furnace zone heated by radiant tubes (RTF) or by resistance, or by induction, or by any combination of these various means. The atmosphere contains 3 to 40% by volume of hydrogen, the balance being nitrogen and unavoidable impurities, the dew point below -30 ° C. In this second zone, the sheet is heated to a temperature T2b of between 760 and 830 ° C. Preferentially, T2b is greater than Ad, which allows faster decarburization due to the presence of carbon in solid solution in the austenite. The time interval between the instant when the sheet is at temperature T1 b and the moment when it reaches temperature T2b must be at least 30 seconds to obtain a decarburization depth p _50% included between 6 and 30 micrometers. These conditions lead to a total reduction of the superficial layer of iron oxide created in the previous step, and the target surface decarburization.

The parcel sheet then enters a holding zone at a holding temperature Tm between T2b and T2b + 40 ° C.

The rest of the process is identical in the three modes described above: the sheet is cooled to a temperature T3 in an atmosphere A4 such that no superficial reoxidation of iron intervenes. For example, an atmosphere containing from 2 to 70% by volume of hydrogen may be used, the balance being nitrogen and unavoidable impurities in the gas, with a dew point of between -60 and -30 ° C. The sheet which subsequently enters the pre-coating bath is therefore totally free of superficial iron oxide. The temperature T3 is close to that of Tbm, temperature of the pre-coating bath, in order to avoid a thermal disturbance of the bath. For this reason, the temperature T3 will be between Tbm-10 ° C and Tbm + 50 ° C. Thus, for a zinc pre-coating, the temperature T3 will be between 450 and 510 ° C. For a pre-coating in a so-called aluminum-silicon bath, the temperature T3 will be between 660 and 720 ° C. The pre-coating may be aluminum or an aluminum-based alloy. In the latter case, the pre-coating, preferably manufactured by continuous quenching, is advantageously an aluminum-silicon alloy comprising, by weight, 7-15% of silicon, 3 to 20% of iron, optionally between 15 and 30 ppm of calcium, the rest being aluminum and unavoidable impurities resulting from the elaboration.

The pre-coating may also be zinc or a zinc alloy. It may be in particular of the type dipped galvanized continuous ("Gl") containing 0.25-0.70% AI, 0.01-0.1% Fe, the balance being zinc and unavoidable impurities resulting of elaboration. The pre-coating can also be galvanized-alloy ("GA") containing 0.15-0.4% AI, 6-15% Fe, the balance being zinc and unavoidable impurities resulting from elaboration. The precoat may also be a zinc-aluminum-magnesium alloy containing 1-15% Al, 0.5-5% Mg, 0.01-0.1% Fe, the balance being zinc and unavoidable impurities resulting from development. This pre-coating may be an alloy containing 4-6% AI, 0.01-0.1% Fe, the balance being zinc and unavoidable impurities resulting from the elaboration.

The pre-coating may also be an aluminum-zinc alloy containing 40-45% Zn, 3-10% Fe, 1-3% Si, the balance being aluminum and unavoidable impurities resulting from the preparation.

The pre-coating may also be composed of a superposition of layers: for example, after dipping a layer of aluminum or aluminum alloy, one or more subsequent deposits of zinc or aluminum may be made. zinc alloy, for example by electrodeposition or by vacuum deposition: PVD (Physical Vapor Deposition) and / or CVD (Chemical Vapor Deposition), these deposition processes being known per se.

At this stage, using the processes described above, a sheet made of a steel substrate with a depth of decarburization p ₅₀ % of between 6 and 30 microns surmounted by a pre-coating, without a coating layer, is obtained. iron oxide present between the substrate and the precoat. FIG. 1 shows an example of such sheet metal, where the steel substrate 1 comprises a specific surface decarburized area 2 surmounted by a pre-coating 1 galvanized galvanized-alloyed.

This sheet is then cut to obtain a blank whose geometry is related to the final geometry of the target part. Optionally, it is possible to cold stamp it so as to approach to a greater or lesser degree of the final geometry of the target part. In the case of a low cold deformation, it may be supplemented by deformation carried out hot, as will be discussed below.

This flat or pre-stamped blank is heated to a temperature T _R capable of conferring a partially or totally austenitic structure on the steel substrate. T _R can be between A _c i (austenitic steel starting temperature at heating) and A _c3 (austenitic end-of-transformation temperature), especially when it is desired to obtain bainitomensitic microstructures after cooling. to the press. The temperature TR will be greater than A _C 3 if one rather aims a microstructure predominantly martensitic in the final part. The heating of the blanks is preferably carried out in an oven under ordinary atmosphere; during this step, the steel of the substrate and the precoat are alloyed. The term "pre-coating" refers to the alloy before heating, and "coating" the alloy layer formed during heating immediately preceding the hot stamping. The furnace heat treatment therefore modifies the nature of the pre-coating and its geometry since the thickness of the final coating is greater than that of the pre-coating. The coating formed by alliation protects the underlying steel from oxidation and additional decarburization and is capable of subsequent hot deformation including in a stamping press. Alliation occurs over the entire thickness of the coating. Depending on the composition of the pre-coating, one or more intermetallic phases are formed in this alloy layer and / or an alloy in the form of a solid solution. The iron enrichment of the coating leads to a rapid rise in its melting point. The formed coatings also have the advantage of being adherent and being adapted to the possible operations of hot shaping and rapid cooling that will follow. The blank is kept at the temperature TR to ensure the homogeneity of the temperature within it. Depending on the thickness of the blank, for example between 0.5 to 4 mm, the holding time at the temperature Ti may vary from 30 seconds to 15 minutes.

The heated blank is then extracted from the furnace and transferred into a tool, this transfer being effected rapidly so as not to cause transformation of the austenite to cooling. According to a variant, the blank is heated in the vicinity of the tooling and then deformed hot without transfer. The blank is then hot stamped so as to obtain the final geometry of the part. Other modes of hot deformation are also possible, for example a forming between rollers usually referred to as "roll forming". In the case where the blank has already been cold-stamped beforehand, the step following the extraction of the blank from the oven can be simply a conformation within a press tooling. In this case, the conformation is characterized by a lower applied force of the tooling on the workpiece and is intended to complete the final geometry of the workpiece and to avoid any deformation during cooling.

Optionally, it is also possible to heat only a portion of the blank, or to cool the stamped part differently in its different zones, these variants leading to the obtaining of non-uniformly hardened parts, some areas being significantly hardened, other areas with less mechanical strength but higher ductility.

After the stamping or shaping step, the part is held in the possibly cooled tooling, so as to ensure its efficient cooling by thermal conduction.

Depending on the cooling rate and the hardenability of the substrate steel, the final microstructure is martensitic or bainitic-martensitic.

By way of non-limiting example, the following results will show the advantageous characteristics conferred by the invention.

Example 1 A 1.2 mm thick steel sheet was supplied, the composition of which is expressed in weight content (%), the remainder being iron and unavoidable impurities resulting from the preparation:

The Ac1 temperature of this steel composition is 724 ° C. The sheet was preheated on the run in a radiant tube furnace under a nitrogen A1 atmosphere containing 4.7% by volume of hydrogen with a dew point of -31 ° C, up to a temperature T1 of 600 ° C from which a water injection is performed so as to obtain an atmosphere A2a with a dew point PR. Various tests were carried out by modifying the flow rate of water injected into the furnace, so as to vary the dew point PR between -27 ° C. (obtained thanks to a relatively small quantity of water injected) and -7 ° C. vs. In all the tests, the sheet was then heated from the temperature T.sub.a to the temperature T2a equal to 780.degree. C. in the atmosphere A2a for a period of 10 seconds, which leads to obtaining a decarburization and a internal selective oxidation of Mn, Si, Al, Cr and Ti. At the temperature T2a, the dew point of the iron / iron oxide equilibrium is + 17 ° C. The sheet then enters a zone of the furnace where it is maintained at the temperature Tm of 780 ° C. under an atmosphere A3 containing nitrogen and 7% of hydrogen, reducing for iron. The sheet is then cooled by passing through another zone of the furnace under an atmosphere containing 10% of hydrogen to a temperature T3 of 470.degree. C. and pre-quenched by dipping in a bath at a temperature Tm of 462.degree. zinc and 0, 125% aluminum and unavoidable impurities. No superficial reoxidation of iron occurs in the maintenance and cooling steps in the atmosphere A4. Immediately after pre-coating, the sheet is heated to a temperature of 540 ° C to obtain a coating galvanized-alloy ("GA"), that is to say containing 9% iron. A sheet not containing an iron oxide layer is thus obtained between the steel substrate and said galvanized-alloy pre-coating. This pre-coated sheet was then cut to obtain blanks suitable for stamping. These were heated to a temperature of 880 ° C in a furnace under ordinary atmosphere. After total residence of 5 minutes in the oven (including a duration of 4 minutes for the heating phase), the blanks were extracted and stamped immediately. After hot stamping, the parts were cooled in press at a speed greater than 30 ° C / s so as to obtain a totally martensitic structure in the steel substrate. The tensile strength Rm obtained on the cured parts is typically of the order of 1500 MPa. The critical bending angle a _c of these pieces was measured by three-point bending test performed with two outer rollers 30 mm in diameter and a central knife of very small radius.

FIG. 6 shows the variation of the critical angle a _c as a function of the dew point PR after water injection from the temperature T1a: when PR is less than -15 ° C., the folding angle obtained has a value less than 55 °, unsatisfactory. When PR exceeds the temperature Te of + 17 ° C, there is a possible risk of not completely reducing the iron oxide during the subsequent maintenance, thus causing the local appearance of coating defects corresponding to the local presence of oxides superficial not reduced. In the field of the invention, the bending angle varies little according to the dew point: between -15 and -7 ° C, the increase is 0.79 ° per ° C on average while the variation is more important below - 15 ° C (1.05 ° C) When PR is between -15 and -10 ° C, we highlight a particularly interesting area since the bending angle is virtually independent of the point Dew. In other words, in this particular range, an undesirable possible fluctuation of the quantity of water injected during oven annealing has no effect on the bending ability after hot stamping, which makes it possible to to guarantee a great stability of the characteristics on the stamped parts and hardened to the press.

Tests have also been carried out by simultaneously varying PR and the temperature T1a, the latter being 720 ° C. (ie Ac1-4 ° C.) or 760 ° C. (Ac1 + 36 ° C.). influence of the temperature T a and the point dew PR on the decarburization depth p _50% before hot stamping, measured by glow discharge spectroscopy: when the dew point is too low, the decarburized depth does not reach the value required by the invention (result found " A "in Figure 7). A sufficiently high dew point, with a temperature T1a slightly lower than Ac1 makes it possible to reach the required depth (result "B") Heating at a higher T1 temperature (Ac1 + 36 ° C.) makes it possible to increase significantly the depth of decarburization p ₅ o _% (result "C")

After polishing and Nital reagent etching of the hot stamped parts obtained, the microstructure under the coating which was obtained by the diffusional bonding between the zinc of the initial pre-coating and the steel of the substrate was observed by optical microscopy: FIG. thus the coating 15 and the underlying steel 16, for annealing with a dew point PR = -27 ° C. Figure 9 illustrates the coating 17 and the underlying steel 18, for annealing with a dew point PR = -7 ° C. Despite the significant difference in folding ability between the two samples (20 °), no significant microstructural differences were found between the two samples after hot stamping, despite the difference in decarburization between them before hot stamping:

FIG. 10 illustrates the variation, before hot stamping, of the carbon content of the two annealed sheets in an A2a atmosphere with a dew point PR of -27 ° C. or -7 ° C. This variation, measured by glow discharge spectrometry in the steel substrate, is expressed in FIG. 10 as a function of the depth under the interface between the steel and the precoat. The measured local content (C) was referred to the nominal carbon content C ₀ so as to obtain the variation of the relative carbon content C / C ₀ . It is observed that the decarburized zones are very different in the two annealing conditions, the decarburization depth p _50% being 15 microns for PR = -7 ° C. and 3 microns for PR = -27 ° C. If we consider the entire decarburized zone, the decarburization depth measured after annealing with PR = -7 ° C is about 35 micrometers higher than that measured after annealing at PR = -27 ° C.

After hot stamping of these sheets, it was determined by the same method the variation of the carbon content under the coating of the pieces thus obtained. Figure 11 illustrates the variation of the relative carbon content C / C ₀ of these parts. It is then demonstrated that the decarburized zone is substantially identical in both annealing conditions. This indicates that furnace heating prior to press hardening treatment leads to diffusion of carbon to the decarburized surface of the steel. The determination of the decarburization after hot stamping does not make it possible to determine that the annealing with PR = -7 ° C will lead to satisfactory folding results while the annealing with PR = -27 ° C. will not satisfy the required level. Although incomplete, this homogenization of the carbon makes it possible, however, to obtain in the steel immediately beneath the coating, a sufficient carbon content to cause martensitic quenching under the cooling conditions associated with hot stamping, as illustrated in FIGS. Figures 8 and 9. However, the intrinsic characteristics of tenacity of the martensite created under these conditions, depend on the decarburization conditions resulting in particular from the choice of the PR temperature. Thus, the effective control of the bending ability of the hot-stamped parts must be achieved on the sheets or blanks before the hot stamping operation, and not after the latter, contrary to what was expected by the skilled person. In addition, the hot-stamped parts made from sheets pre-coated zinc or zinc alloy decarburized according to the invention, have a particular aptitude for spot resistance welding: indeed, after heating and hot stamping, it is possible to note the presence of a decarburized layer under the coating. It is known that resistance welding leads to a very high local temperature rise since the fusion is reached within the molten core which constitutes the connection between the welded elements. In welded joints made on conventional hot-stamped parts, the austenitic grain boundaries can be weakened by penetration of the zinc coating, which is then liquid because of the rise in temperature during welding. According to the invention, the presence of a zone that is very depleted of carbon under the coating leads to a local increase in the temperature of Ac3 transformation into austenite during heating. Depending on the carbon content, the high temperature structure then consists of ferrite microstructure or a mixture of ferrite and austenite. In the presence of liquid zinc, this microstructure has a lower susceptibility to cracking than the austenitic structure.

Example 2

Pre-coated sheets of Zn were made by the method described above, except that they were 1.8 mm thick and were not heated to 540 ° C after coating. soaked, so that their coating is galvanized and not galvanized-alloyed.

The manufacturing conditions were selected so as to obtain a sheet with a decarburized depth p o _{_5%} to 6 micrometers. These sheets were cut to obtain blanks that were austenitized at a temperature of 880 ° C in a furnace under ordinary atmosphere. After a total residence of up to 10 minutes in the oven, the blanks were extracted, stamped immediately hot and cured in press. The following table shows the variation of the critical bending angle a _c as a function of the total residence time of the part in the oven.

It appears that the blanks can stay up to 7 minutes in the oven before being hot stamped, while meeting the requirements. This solves the problems encountered on the hot stamping lines, when an incident on the line forced to keep the blanks in the oven longer than expected. The invention allows this flexibility, avoiding discarding blanks. In addition, it will be observed that beyond 7 minutes, the increase in residence time leads only to a very small decrease in the bending angle, which indicates that the method according to the invention has great safety guarantees in case of drift compared with the nominal parameters of heat treatment during hot stamping, and provides a high reproducibility of the mechanical characteristics of the parts.

Thus, the invention allows the manufacture of pre-coated sheets and coated parts with very high characteristics of strength and folding ability, with good isotropy, under very satisfactory economic conditions. These parts will be used profitably as structural parts or reinforcements in the field of automotive construction.

Claims

Pre-coated laminated sheet for the manufacture of hardened press-hardened parts, composed of a heat-treatable steel substrate containing a carbon content C ₀ of between 0.07% and 0.5%, said content being expressed by weight, and a metal pre-coating at least on the two main faces of said steel substrate, characterized in that said substrate comprises a decarburized zone on the surface of each of said two main faces, the depth p ₅ o < _% of said decarburized zone being between 6 and 30 micrometers, preferably between 9 and 30 micrometers, and very preferably between 12 and 30 micrometers, p ₅ o _% being the depth at which the carbon content is equal to 50% of said content C ₀ , and in that said sheet does not contain an iron oxide layer between said substrate and said metal pre-coating.

Pre-coated sheet according to claim 1 characterized in that said metal pre-coating is aluminum or an aluminum alloy.

Pre-coated sheet according to claim 1 characterized in that said metal pre-coating is zinc or a zinc alloy.

Pre-coated sheet according to claim 1 characterized in that said metal pre-coating is composed of a layer of aluminum or an aluminum alloy, topped with a layer of zinc or a zinc alloy

Pre-coated sheet according to any one of claims 1 to 4 characterized in that the composition of said steel substrate comprises, the contents being expressed by weight:

0.07% <C <0.5% 0.5% <Mn <3%

0.02% <If <0.5%

0.01% <Cr <1%

Ti <0.2%

AI <0.25%

S <0.05%

P≤0,1%

0.0005% <B <0.010%,

optionally 0.0005% <Ca <0.005%,

the remainder of the composition consisting of iron and unavoidable impurities resulting from the elaboration.

Pre-coated sheet according to any one of claims 1 to 4, characterized in that the composition of said steel substrate comprises, the contents being expressed by weight:

0.09% <C <0.38%

0.8% <Mn <1.5%

0.1% <If <0.35%

0.01% <Cr <0.3%

0.02% <Ti <0.1%

0.001% ≤ Al <0.25%

S <0.05%

P <0.1%

0.002% <B <0.005%,

optionally 0.0005% <Ca <0.005%,

the remainder of the composition consisting of iron and unavoidable impurities resulting from the elaboration Pre-coated sheet according to any one of claims 1 to 6, characterized in that the composition of said steel substrate comprises, the content being expressed by weight:

0.15% <C <0.25%

A method of manufacturing a coated and cured steel part, comprising the successive steps according to which:

supplying a rolled steel sheet for heat treatment containing a carbon content C ₀ of between 0.07% and 0.5%, then

said laminated sheet is annealed so as to obtain, after annealing, a decarburization of the surface of said sheet to a depth p _50% of between 6 and 30 micrometers, p _50% being the depth at which the carbon content is equal to 50% of said content C ₀ , and so as to obtain a sheet totally free of iron oxide layer on its surface, and then

a pre-coating of metal or metal alloy is carried out on said annealed sheet acting as a substrate, then

said pre-coated sheet is cut to obtain a blank, then

the said blank is optionally cold-pressed, then

said blank is heated to a temperature T _R in an oven so as to at least partially impart an austenitic structure to said steel, and then

said heated blank is extracted from the furnace and transferred to a press or a shaping device, and

it deforms hot or hot gauge said blank to obtain a room, then

said part is cooled in said press or said shaping device to impart to it by quenching a martensitic or bainito-martensitic microstructure. Manufacturing method according to claim 8 characterized in that said pre-coating is carried out continuously by dipping by bathing. Manufacturing method according to claim 8 or 9 characterized in that said pre-coating is aluminum or a aluminum alloy Manufacturing method according to claim 8 or 9 characterized in that said pre-coating is zinc or a zinc alloy Manufacturing process according to claim 8 or 9 characterized in that said metal pre-coating is composed of an aluminum or aluminum alloy layer, surmounted by a layer of zinc or a zinc alloy. A manufacturing method according to any one of claims 8 to 12, characterized in that said depth pso is between 9 and 30 micrometers, preferably between 12 and 30 micrometers

Manufacturing method according to any one of claims 8 to 13, characterized in that the composition of said steel substrate comprises, the contents being expressed by weight:

0.07% <C <0.5%

0.5% <Mn <3%

0.02% <If <0.5%

0.01% <Cr <1%

Ti <0.2%

Al <0.25%

S <0.05%

P <0.1%

0.0005% <B <0.010%,

optionally 0.0005% <Ca <0.005%, the remainder of the composition consisting of iron and unavoidable impurities resulting from the elaboration.

Manufacturing method according to any one of claims 8 to 14, characterized in that the composition of said steel substrate comprises, the contents being expressed by weight:

0.09% <C <0.38%

0.8% <Mn <1.5%

0.1% <If <0.35%

0.01% <Cr <0.3%

0.02% ≤Ti <0.1%

0.001% ≤ Al <0.25%

S <0.05%

P <0.1%

0.002% <B <0.005%,

optionally 0.0005% <Ca <0.005%,

the remainder of the composition consisting of iron and unavoidable impurities resulting from the production process according to any one of claims 8 to 15, characterized in that the composition of said steel substrate comprises, the content being expressed by weight :

0, 15% <C <0.25%

Manufacturing method according to any one of claims 8 to 16 characterized in that said temperature T _R is greater than or equal to the temperature A _{c3 of} said steel.

Manufacturing method according to any one of claims 8 to 17 characterized in that said annealing conditions comprise the following successive steps: - After supplying said rolled steel sheet, is preheated in the parade in a radiant tube furnace, or a resistance furnace, or an induction furnace, or a furnace combining at least two of these means, said sheet rolled up to at a temperature T1a of between 600 ° C. and Ac1 + 40 ° C., Ad denoting the austenitic transformation start temperature at heating said steel, in an area of said furnace in which the atmosphere A1 contains from 2 to 15% by volume of hydrogen, preferably 3-5% by volume of hydrogen, the balance being nitrogen and unavoidable impurities, with a dew point between -60 and -15 ° C, and then

said sheet of temperature T1a is heated to a temperature T2a of between 720 and 860 ° C., an injection of at least one element chosen from liquid water, steam water or oxygen, being carried out in said oven from said temperature T1 a to obtain, in the section of the furnace between said temperature T1a and said temperature T2a, an atmosphere A2a with a dew point PR of between -15 ° C and the temperature Te the dew point of the iron / iron oxide equilibrium, the time interval between the instant when the sheet is at the temperature T1 a and the instant when said sheet reaches the temperature T2a, being greater than or equal to 30 seconds and then

said sheet is maintained at a temperature Tm between T2a and T2a + 40 ° C, in a reducing atmosphere A3 for iron, and then said sheet is cooled in an atmosphere A4 such that no surface reoxidation of the iron intervenes, until at a temperature T3, then

pre-coating of said sheet by a dip in a metal bath at the temperature Tbm, provided that said temperature T3 is between Tbm-10 ° C and Tbm + 50 ° C.

Process according to Claim 18, characterized in that the said dew point PR is between -15 and + 17 ° C. 0 Process according to claim 18, characterized in that said dew point PR is between -15 and -10 ° C. 1 manufacturing method according to any one of claims 8 to 17 characterized in that said annealing conditions comprise the following successive steps:

- After supplying said rolled steel sheet, is preheated in the parade in a radiant tube furnace, or a resistance furnace, or an induction furnace, or a furnace combining at least two of these means, said sheet rolled up to at a temperature T1a of between 600 ° C. and Ac1 + 40 ° C., Ad denoting the austenitic transformation start temperature at heating said steel, in an area of said furnace in which the atmosphere A1 contains from 2 to 15% by volume of hydrogen, preferably 3-5% by volume of hydrogen, the balance being nitrogen and unavoidable impurities, with a dew point between -60 and -15 ° C, and then

said sheet of temperature T1a is heated to a temperature T2a of between 720 and 860 ° C., an injection of at least one element chosen from liquid water, steam water or oxygen, being carried out in said oven from said temperature T1a to obtain, in the section of the furnace between said temperature T1a and said temperature T2a, an oxidizing atmosphere A2b for the iron, the time interval between the instant when the sheet is at the temperature T1a and the moment when said sheet reaches the temperature T2a, being greater than or equal to 30 seconds, then

said sheet is maintained at a temperature Tm between T2a and T2a + 40 ° C, under a reducing atmosphere A3 for iron, the complete reduction of the iron layer formed in said atmosphere A2b, occurring at the latest at the end of maintaining at said temperature Tm, then

said sheet is cooled in an atmosphere A4 such that no superficial reoxidation of the iron takes place, up to a temperature T3, then a precoating of said sheet is carried out by a quenching passage in a metal bath at the temperature Tbm, provided that said temperature T3 is between Tbm-10 ° C and Tbm + 50 ° C. Manufacturing process according to any one of claims 18 to 21, characterized in that said temperature T1a is greater than Ad, austenitic transformation temperature when heating said steel substrate. Manufacturing method according to any one of claims 8 to 17, characterized in that said annealing conditions comprise the following successive steps:

- After supplying said steel sheet, said laminated sheet is preheated in a furnace in an oven, said preheating being carried out in an area of a heated oven with direct flames, said sheet being preheated to a temperature T1b between 550 and 750 ° C in an atmosphere resulting from the combustion of a mixture of air and natural gas whose air / gas ratio is between 1 and 1, 2, then

said sheet of temperature T1 b is heated up to a temperature T2b of between 760 and 830 ° C. in a second furnace zone heated by radiant tubes, or by resistance, or by induction, or by any combination at least two of these means, the atmosphere of which contains 3 to 40% by volume of hydrogen, the balance being nitrogen and unavoidable impurities, the dew point being below -30 ° C, time interval between the instant when the sheet is at said temperature T1 b and the moment when said sheet reaches said temperature T2b, being at least 30 seconds, then

said sheet is maintained at a temperature Tm between T2b and T2b + 40 ° C, under a reducing atmosphere A3 for iron, and then

said sheet is cooled in an atmosphere A4 such that no surface reoxidation intervenes, up to a temperature T3, then a pre-coating of said sheet is carried out by a quenching step in a metal bath at the temperature Tbm, it being understood that said temperature T3 is between Tbm-10 ° C and Tbm + 50 ° C.

Manufacturing method according to claim 23, characterized in that said temperature T2b is greater than Ac1